KR102204111B1 - Compound and organic photoelectronic device and image sensor - Google Patents

Abstract

An organic photoelectric device including a compound represented by Chemical Formula 1, a first electrode and a second electrode facing each other, and an active layer disposed between the first electrode and the second electrode and including the compound represented by Chemical Formula 1, and the organic photoelectric It relates to an image sensor comprising a device.

Description

Compound, organic photoelectric device, and image sensor {COMPOUND AND ORGANIC PHOTOELECTRONIC DEVICE AND IMAGE SENSOR}

It relates to compounds, organic photoelectric devices and image sensors.

A photoelectric device is a device that converts light into an electric signal using a photoelectric effect, and includes a photodiode and a phototransistor, and may be applied to an image sensor.

Image sensors including photodiodes have a higher resolution as days go by, and accordingly, a pixel size is decreasing. In the case of a silicon photodiode, which is mainly used at present, since the size of the pixel decreases and the absorption area decreases, sensitivity may decrease. Accordingly, organic materials that can replace silicon are being studied.

Since the organic material has a high extinction coefficient and can selectively absorb light in a specific wavelength region according to its molecular structure, it is very advantageous in improving sensitivity and high integration because it can simultaneously replace a photodiode and a color filter.

One embodiment provides a compound capable of selectively absorbing light in a green wavelength region.

Another embodiment provides an organic photoelectric device capable of selectively absorbing light in a green wavelength region and improving efficiency.

Another embodiment provides an image sensor including the organic photoelectric device.

According to one embodiment, a compound represented by the following formula 1 is provided.

[Formula 1]

In Formula 1,

R ¹ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted A ringed C3 to C30 heteroaryl group, a substituted or unsubstituted C6 to C30 arylamine group, an amine group, a halogen group, a hydroxy group, a cyano group, a cyanovinyl group, a dicyanovinyl group, or a combination thereof,

R ² to R ⁷ are each independently present or two adjacent to each other form a fused ring, and hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heteroaryl group, substituted or unsubstituted C1 to C30 carbonyl group, substituted or unsubstituted C6 to C30 arylamine A group, an amine group, a halogen group, a hydroxy group, a cyano group, a cyanovinyl group, a dicyanovinyl group, or a combination thereof,

X ¹ and X ² are each independently a halogen group, a halogen-containing group, or a combination thereof.

The compound may have a maximum absorption wavelength (λ _max ) at about 500 nm to 600 nm.

The compound may exhibit an absorption curve having a full width at half maximum (FWHM) of about 50 nm to 150 nm in a thin film state.

The compound may have a HOMO level of about 4.3 to 7.0 eV and an energy band gap of about 1.9 to 3.1 eV.

In Formula 1, X ¹ and X ² may each be fluorine, and R ¹ may be a substituted or unsubstituted C6 to C30 aryl group, a cyano group, or a combination thereof.

The compound may be a compound represented by any one of the following Formulas 1a to 1n.

[Formula 1a] [Formula 1b] [Formula 1c] [Formula 1d]

[Formula 1e] [Formula 1f] [Formula 1g]

[Formula 1h] [Formula 1i] [Formula 1j]

[Formula 1k] [Formula 1l]

[Formula 1m] [Formula 1n]

According to another embodiment, there is provided an organic photoelectric device including a first electrode and a second electrode facing each other, and an active layer disposed between the first electrode and the second electrode and including a compound represented by Formula 1 below. .

[Formula 1]

In Formula 1,

R ¹ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted Ringed C3 to C30 heteroaryl group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C6 to C30 arylamine group, amine group, halogen group, hydroxy group, cyano group, cyanovinyl group, dicyano Vinyl group or a combination thereof,

R ² to R ⁷ are each independently present or two adjacent to each other form a fused ring, and hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 heterocycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heteroaryl group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C30 carbonyl group, substituted or unsubstituted C6 to C30 arylamine group, amine Group, halogen group, hydroxy group, cyano group, cyanovinyl group, dicyanovinyl group, or a combination thereof,

X ¹ and X ² are each independently a halogen group, a halogen-containing group, or a combination thereof.

The active layer may have a maximum absorption wavelength (λ _max ) in about 500 nm to 600 nm.

The active layer may exhibit an absorption curve having a half width of about 50 nm to 150 nm.

The compound may have a HOMO level of about 4.3 to 7.0 eV and an energy band gap of about 1.9 to 3.1 eV.

In Formula 1, X ¹ and X ² may each be fluorine, and R ¹ may be a substituted or unsubstituted C6 to C30 aryl group, a cyano group, or a combination thereof.

The compound represented by Formula 1 may be represented by any one of the following Formulas 1a to 1p.

[Formula 1a] [Formula 1b] [Formula 1c] [Formula 1d]

[Formula 1e] [Formula 1f] [Formula 1g]

[Formula 1h] [Formula 1i] [Formula 1j]

[Formula 1k] [Formula 1l] [Formula 1m] [Formula 1n]

[Formula 1o] [Formula 1p]

The active layer may further include a p-type semiconductor compound or an n-type semiconductor compound.

The p-type semiconductor compound may include at least one of a compound represented by Formula 2 below and a compound represented by Formula 3 below.

[Formula 2]

In Chemical Formula 2,

R ⁸ to R ¹⁹ are Each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, substituted Or an unsubstituted C3 to C30 heteroaryl group, a substituted or unsubstituted C1 to C30 alkoxy group, a halogen atom, or a combination thereof,

[Formula 3]

In Chemical Formula 3,

R ²⁰ to R ³¹ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, a halogen atom, a halogen-containing group Or a combination thereof,

X is an anion.

The active layer may selectively absorb light in a green wavelength region.

The active layer may include an intrinsic layer including the compound represented by Chemical Formula 1.

The active layer may further include at least one of a p-type layer located on one surface of the intrinsic layer and an n-type layer located on the other surface of the intrinsic layer.

According to another embodiment, an image sensor including the organic photoelectric device is provided.

The image sensor is a semiconductor substrate in which a plurality of first photo-sensing elements for detecting light in a blue wavelength region and a plurality of second photo-sensing elements for detecting light in a red wavelength region are integrated, and is positioned above the semiconductor substrate A color filter layer comprising a blue filter selectively absorbing light in a wavelength region and a red filter selectively absorbing light in a red wavelength region, and is positioned above the color filter layer and selectively absorbs light in a green wavelength region. It may include the organic photoelectric device.

An organic photoelectric device and an image sensor capable of improving efficiency by providing a compound capable of selectively absorbing light in a green wavelength region and increasing wavelength selectivity in a green wavelength region by the compound are provided.

1 is a cross-sectional view showing an organic photoelectric device according to an embodiment,
2 is a cross-sectional view showing an organic photoelectric device according to another embodiment,
3 is a cross-sectional view showing an organic CMOS image sensor according to an embodiment,
4 is a cross-sectional view showing an organic CMOS image sensor according to another embodiment,
5 is a photograph showing the thin film properties of the compound obtained in Synthesis Example 3,
6 to 11 are graphs showing external quantum efficiency (EQE) according to wavelength and voltage of organic photoelectric devices according to Examples 1 to 6, respectively,
12 is a graph showing changes in current density after leaving the organic photoelectric device according to Example 4 at 120° C. for 30 minutes,
13 is a graph showing changes in current density after leaving the organic photoelectric device according to Example 5 at 120° C. for 30 minutes.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art may easily implement the present invention. However, the present invention may be implemented in various different forms, and is not limited to the embodiments described herein.

Unless otherwise defined in the specification, the term'substituted' means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, amidino Group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C4 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, C6 to It means substituted with a substituent selected from a C15 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, and combinations thereof.

In addition, unless otherwise defined in the specification,'hetero' means containing 1 to 3 heteroatoms selected from N, O, S, and P.

In the drawings, the thicknesses are enlarged to clearly express various layers and regions. The same reference numerals are assigned to similar parts throughout the specification. When a part of a layer, film, region, plate, etc. is said to be "on" another part, this includes not only the case where the other part is "directly above", but also the case where there is another part in the middle. Conversely, when one part is "directly above" another part, it means that there is no other part in the middle.

In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present embodiment, and the same reference numerals are used for the same or similar components throughout the specification.

Hereinafter, a compound according to an embodiment will be described.

The compound according to an embodiment is represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted A ringed C3 to C30 heteroaryl group, a substituted or unsubstituted C6 to C30 arylamine group, an amine group, a halogen group, a hydroxy group, a cyano group, a cyanovinyl group, a dicyanovinyl group, or a combination thereof,

R ² to R ⁷ are each independently present or two adjacent to each other form a fused ring, and hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heteroaryl group, substituted or unsubstituted C1 to C30 carbonyl group, substituted or unsubstituted C6 to C30 arylamine A group, an amine group, a halogen group, a hydroxy group, a cyano group, a cyanovinyl group, a dicyanovinyl group, or a combination thereof,

X ¹ and X ² are each independently a halogen group, a halogen-containing group, or a combination thereof.

The compound is a compound that selectively absorbs light in a green wavelength region, and may have a maximum absorption wavelength (λ _max ) in about 500 nm to 600 nm.

The compound may exhibit an absorption curve having a relatively small full width at half maximum (FWHM) of about 50 nm to 150 nm in a thin film state. Here, the half-value width is the width of the wavelength corresponding to half of the maximum absorption point. If the half-value width is small, it means that the wavelength selectivity is high by selectively absorbing light in a narrow wavelength range. By having a half width of the above range, selectivity for a green wavelength region can be improved.

The compound may have a HOMO level of about 4.3 to 7.0 eV, and may have an energy band gap of about 1.9 to 3.1 eV. By having the HOMO level and energy band gap in the above range, it can be applied as an n-type or p-type semiconductor that effectively absorbs light in the green wavelength region, and accordingly, it can have high external quantum efficiency (EQE), photoelectric conversion Efficiency can be improved.

For example, in Formula 1, X ¹ and X ² may each be fluorine.

For example, in Formula 1, R ¹ may be a substituted or unsubstituted C6 to C30 aryl group, a cyano group, or a combination thereof. The aryl group may be, for example, a phenyl group.

The compound may be, for example, represented by any one of Formulas 1a to 1n, but is not limited thereto.

[Formula 1a] [Formula 1b] [Formula 1c] [Formula 1d]

[Formula 1e] [Formula 1f] [Formula 1g]

[Formula 1h] [Formula 1i] [Formula 1j]

[Formula 1k] [Formula 1l]

[Formula 1m] [Formula 1n]

Hereinafter, an organic photoelectric device according to an embodiment including the compound will be described with reference to the drawings.

1 is a cross-sectional view illustrating an organic photoelectric device according to an embodiment.

Referring to FIG. 1, an organic photoelectric device 100 according to an embodiment includes a first electrode 10 and a second electrode 20 facing each other, and between the first electrode 10 and the second electrode 20. It includes an active layer 30 located at.

One of the first electrode 10 and the second electrode 20 is an anode and the other is a cathode. At least one of the first electrode 10 and the second electrode 20 may be a light-transmitting electrode, and the light-transmitting electrode includes, for example, indium tin oxide (ITO) or indium zinc oxide (IZO). It may be made of the same transparent conductor, or a thin single layer or multiple layers of metal thin film. When one of the first electrode 10 and the second electrode 20 is an opaque electrode, it may be made of an opaque conductor such as aluminum (Al).

The active layer 30 is a layer containing a p-type semiconductor material and an n-type semiconductor material to form a pn junction, and generates excitons by receiving light from the outside, and then converting the generated excitons into holes and electrons. It is a separating layer.

The active layer 30 includes a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

R ¹ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted Ringed C3 to C30 heteroaryl group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C6 to C30 arylamine group, amine group, halogen group, hydroxy group, cyano group, cyanovinyl group, dicyano Vinyl group or a combination thereof,

R ² to R ⁷ are each independently present or two adjacent to each other form a fused ring, and hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 heterocycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heteroaryl group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C30 carbonyl group, substituted or unsubstituted C6 to C30 arylamine group, amine Group, halogen group, hydroxy group, cyano group, cyanovinyl group, dicyanovinyl group, or a combination thereof,

X ¹ and X ² are each independently a halogen group, a halogen-containing group, or a combination thereof.

The compound is a compound that selectively absorbs light in a green wavelength region, and the active layer 30 including the compound can selectively absorb light of a green wavelength having a maximum absorption wavelength (λ _max ) at about 500 nm to 600 nm. have.

The active layer 30 may exhibit an absorption curve having a relatively small half width (FWHM) of about 50 nm to 150 nm. Accordingly, the active layer 30 may have high selectivity for light in the green wavelength region.

The compound may have a HOMO level of about 4.3 to 7.0 eV, and may have an energy band gap of about 1.9 to 3.1 eV. By having the HOMO level and energy band gap in the above range, it can be applied as an n-type or p-type semiconductor that effectively absorbs light in a green wavelength region.

For example, in Formula 1, X ¹ and X ² may each be fluorine.

For example, in Formula 1, R ¹ may be a substituted or unsubstituted C6 to C30 aryl group, a cyano group, or a combination thereof. The aryl group may be, for example, a phenyl group.

The compound may be, for example, represented by any one of Formulas 1a to 1p, but is not limited thereto.

[Formula 1a] [Formula 1b] [Formula 1c] [Formula 1d]

[Formula 1e] [Formula 1f] [Formula 1g]

[Formula 1h] [Formula 1i] [Formula 1j]

[Formula 1k] [Formula 1l] [Formula 1m] [Formula 1n]

[Formula 1o] [Formula 1p]

The compound may be applied as an n-type semiconductor or a p-type semiconductor in the active layer 30. When the compound is applied as an n-type semiconductor, it may further include a p-type semiconductor for forming a pn junction together with the n-type semiconductor. When the compound is applied as a p-type semiconductor, a pn junction is formed with the p-type semiconductor. It may further include an n-type semiconductor for forming.

For example, when the compound is applied as an n-type semiconductor, it may further include a p-type semiconductor represented by Formula 2 below.

[Formula 2]

In Chemical Formula 2,

R ⁸ to R ¹⁹ are Each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, substituted Or an unsubstituted C3 to C30 heteroaryl group, a substituted or unsubstituted C1 to C30 alkoxy group, a halogen atom, or a combination thereof.

The compound represented by Formula 2 may be, for example, at least one of the compounds represented by Formulas 2a to 2h, but is not limited thereto.

[Formula 2a] [Formula 2b] [Formula 2c]

[Formula 2d] [Formula 2e] [Formula 2f]

[Formula 2g] [Formula 2h]

For example, when the compound is applied as an n-type semiconductor, it may further include a p-type semiconductor represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

R ²⁰ to R ³¹ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, a halogen atom, a halogen-containing group Or a combination thereof,

X is an anion.

The compound represented by Formula 3 may be, for example, at least one of the compounds represented by Formulas 3a to 3e, but is not limited thereto.

[Formula 3a] [Formula 3b] [Formula 3c]

[Formula 3d] [Formula 3e]

The active layer 30 may be a single layer or a plurality of layers. The active layer 30 is, for example, an intrinsic layer (I layer), a p-type layer/I layer, an I-layer/n-type layer, a p-type layer/I-layer/n-type layer, a p-type layer/n-type layer, etc. It can be a combination.

The intrinsic layer (I layer) may be included by mixing the p-type semiconductor and the n-type semiconductor at a thickness ratio of about 1:100 to about 100:1. Within the above range may be included in a thickness ratio of about 1:50 to 50:1, may be included in a thickness ratio of about 1:10 to 10:1 within the range, and included in a thickness ratio of about 1:1 I can. Since the p-type semiconductor and the n-type semiconductor have a composition ratio within the above range, it is advantageous for effective exciton generation and pn junction formation.

The p-type layer may include the p-type semiconductor, and the n-type layer may include the n-type semiconductor.

The active layer 30 may have a thickness of about 1 nm to 500 nm. It may have a thickness of about 5nm to 300nm within the above range. By having a thickness in the above range, it is possible to effectively absorb light and effectively separate and transfer holes and electrons, thereby effectively improving photoelectric conversion efficiency.

In the organic photoelectric device 100, when light is incident from the side of the first electrode 10 and/or the second electrode 20 and the active layer 30 absorbs light in a predetermined wavelength range, excitons may be generated therein. The excitons are separated into holes and electrons in the active layer 30, and the separated holes move toward the anode, which is one of the first electrode 10 and the second electrode 20, and the separated electrons are separated from the first electrode 10 and the second electrode. 2 The electrode 20 moves to the other of the cathode, so that a current can flow through the organic photoelectric device.

Hereinafter, an organic photoelectric device according to another embodiment will be described with reference to FIG. 2.

2 is a cross-sectional view illustrating an organic photoelectric device according to another embodiment.

Referring to FIG. 2, the organic photoelectric device 100 according to the present embodiment includes a first electrode 10 and a second electrode 20 facing each other, and the first electrode 10 and the first electrode 10 It includes an active layer 30 positioned between the two electrodes 20.

However, unlike the above-described embodiment, the organic photoelectric device 100 according to the present embodiment has a charge auxiliary layer between the first electrode 10 and the active layer 30 and between the second electrode 20 and the active layer 30, respectively. 40, 50). The charge auxiliary layers 40 and 50 facilitate the movement of holes and electrons separated in the active layer 30 to increase efficiency.

The charge auxiliary layers 40 and 50 are a hole injecting layer (HIL) that facilitates hole injection, a hole transporting layer (HTL) that facilitates hole transport, and a hole-transporting layer (HTL) that prevents the movement of electrons. An electron blocking layer (EBL), an electron injecting layer (EIL) that facilitates the injection of electrons, an electron transporting layer (ETL) that facilitates the transport of electrons, and the movement of holes It may include at least one selected from the blocking hole blocking layer (HBL).

The charge auxiliary layers 40 and 50 may include, for example, an organic material, an inorganic material, or an organic-inorganic material. The organic material may be an organic compound having hole or electronic properties, and the inorganic material may be a metal oxide such as molybdenum oxide, tungsten oxide, or nickel oxide.

The hole transport layer (HTL) is, for example, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), PEDOT:PSS), polyarylamine, Poly(N-vinylcarbazole), polyaniline, polypyrrole, N,N,N',N'-tetrakis(4-methoxyphenyl)-benzidine (N, N,N',N'-tetrakis(4-methoxyphenyl)-benzidine, TPD), 4-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl(4-bis[N-(1 -naphthyl)-N-phenyl-amino]biphenyl, α-NPD), m-MTDATA, 4,4′,4″-tris (N-carbazolyl)-triphenylamine (4,4′,4″-tris (N-carbazolyl)-triphenylamine, TCTA), and one selected from a combination thereof, but is not limited thereto.

The electron blocking layer (EBL) is, for example, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate):poly(styrenesulfonate), PEDOT:PSS), polyarylamine , Poly(N-vinylcarbazole), polyaniline, polypyrrole, N,N,N',N'-tetrakis(4-methoxyphenyl)-benzidine (N ,N,N',N'-tetrakis(4-methoxyphenyl)-benzidine, TPD), 4-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl(4-bis[N-( 1-naphthyl)-N-phenyl-amino]biphenyl, α-NPD), m-MTDATA, 4,4′,4″-tris(N-carbazolyl)-triphenylamine(4,4′,4″- Tris (N-carbazolyl)-triphenylamine, TCTA) and one selected from a combination thereof may be included, but the present invention is not limited thereto.

The electron transport layer (ETL) is, for example, 1,4,5,8-naphthalene-tetracarboxylic dianhydride (1,4,5,8-naphthalene-tetracarboxylic dianhydride, NTCDA), bathocuproine (BCP). ), LiF, Alq3, Gaq3, Inq3, Znq2, Zn(BTZ)2, BeBq2, and combinations thereof, but are not limited thereto.

The hole blocking layer (HBL) is, for example, 1,4,5,8-naphthalene-tetracarboxylic dianhydride (1,4,5,8-naphthalene-tetracarboxylic dianhydride, NTCDA), vasocuproin (BCP) , LiF, Alq3, Gaq3, Inq3, Znq2, Zn(BTZ)2, BeBq2, and one selected from a combination thereof, but is not limited thereto.

One of the charge auxiliary layers 40 and 50 may be omitted.

The organic photoelectric device may be applied to a solar cell, an image sensor, a photo detector, an optical sensor, and an organic light emitting diode, but is not limited thereto.

Hereinafter, an example of an image sensor to which the organic photoelectric device is applied will be described with reference to the drawings. Here, an organic CMOS image sensor will be described as an example of the image sensor.

3 is a cross-sectional view illustrating an organic CMOS image sensor according to an embodiment.

3 exemplarily illustrates adjacent blue, green, and red pixels, but is not limited thereto.

Referring to FIG. 3, an organic CMOS image sensor 300 according to an embodiment includes a semiconductor substrate 310 in which photo-sensing elements 50B and 50R, a transfer transistor (not shown), and a charge storage 55 are integrated. , A lower insulating layer 60, a color filter 70, an upper insulating layer 80, and an organic photoelectric device 100.

The semiconductor substrate 310 may be a silicon substrate, and the photo-sensing element 50, a transfer transistor (not shown), and a charge storage 55 are integrated. The photo-sensing element 50 may be a photodiode.

The photo-sensing elements 50B and 50R, the transfer transistor and/or the charge storage 55 may be integrated for each pixel. As an example, the photo-sensing elements 50B and 50R are blue and red pixels. And the charge storage 55 may be included in the green pixel.

The photo-sensing elements 50B and 50R sense light and the sensed information may be transferred by a transfer transistor, and the charge storage 55 is electrically connected to the organic photoelectric device 100 to be described later, and the charge storage 55 ) Can be transferred by the transfer transistor.

A metal wiring (not shown) and a pad (not shown) are also formed on the semiconductor substrate 310. The metal wiring and the pad may be made of a metal having a low specific resistance, such as aluminum (Al), copper (Cu), silver (g), and alloys thereof, in order to reduce signal delay, but is not limited thereto. However, it is not limited to the above structure, and metal wires and pads may be located under the photo-sensing elements 50B and 50R.

A lower insulating layer 60 is formed on the metal wiring and the pad. The lower insulating layer 60 may be made of an inorganic insulating material such as silicon oxide and/or silicon nitride, or a low-k material such as SiC, SiCOH, SiCO, and SiOF. The lower insulating layer 60 has a trench that exposes the charge storage 55. The trench may be filled with filler material.

A color filter 70 is formed on the lower insulating layer 60. The color filter 70 includes a blue filter 70B formed in a blue pixel and a red filter 70R formed in a red pixel. In this embodiment, an example in which a green filter is not provided is described, but a green filter may be provided in some cases.

An upper insulating layer 80 is formed on the color filter 70. The upper insulating layer 80 is flattened by removing a step difference due to the color filter 50. The upper insulating layer 80 and the lower insulating layer 60 have a contact hole (not shown) exposing the pad and a through hole 85 exposing the charge storage 55 of the green pixel.

The above-described organic photoelectric device 100 is formed on the upper insulating layer 80. The organic photoelectric device 100 includes a first electrode 10, an active layer 30, and a second electrode 20 as described above.

Both the first electrode 10 and the second electrode 20 may be transparent electrodes, and the active layer 30 may selectively absorb light in the green wavelength region as described above and replace the color filter of the green pixel. I can.

Light incident from the side of the second electrode 20 can be photoelectrically converted by mainly absorbing light in the green wavelength region in the active layer 30, and light in the remaining wavelength region passes through the first electrode 10 to pass through the first electrode 10 and pass through the photosensitive element ( 50) can be sensed.

4 is a cross-sectional view illustrating an organic CMOS image sensor according to another embodiment.

Referring to FIG. 4, the organic CMOS image sensor 300 according to the present embodiment is integrated with photo-sensing elements 50B and 50R, a transfer transistor (not shown), and a charge storage 55, as in the above-described embodiment. The semiconductor substrate 310, the lower insulating layer 60, the color filters 70B and 70R, the upper insulating layer 80, and the organic photoelectric device 100 are included.

However, unlike the above-described embodiment, the organic photoelectric device 100 further includes charge auxiliary layers 40 and 50. The charge auxiliary layers 40 and 50 are as described above, and any one of the charge auxiliary layers 40 and 50 may be omitted.

The embodiments of the present invention described above will be described in more detail through the following examples. However, the following examples are for illustrative purposes only and do not limit the scope of the present invention.

Synthesis example

Synthesis example One

[Chemical Formula 1m]

2-Chloro-5-benzoyl in 60 ml CH ₂ Cl ₂ - dissolving the pyrrole (2-chlro-5-benzoyl -pyrrole) 1.1 g and 1.5 mL POCl _3, the reaction mixture was stirred for 3 hours at room temperature. Subsequently, 2.00 g of 2,4-dimethyl-3-ethylpyrrole was added to this solution, followed by additional stirring for 36 hours, followed by washing and drying. After dissolving the obtained material in toluene, a trace amount of triethylamine was added, followed by stirring at room temperature for 1 hour. Then, 1.8 mL of BF ₃ OEt ₂ was added and reacted at 100° C. for 10 hours. Then, vacuum drying after washing. The obtained material was dissolved in 20 ml of acetonitrile, 170 ul of propane-1-amine was added and refluxed for 10 hours while stirring, and the obtained material was recrystallized to obtain the above formula 1m in powder form. Get the represented compound.

MALD-TOF: 409.13 (M+), 409.21 (calculated) for C ₂₃ H ₂₆ BF ₂ N ₃ O,

¹ H NMR (CDCl, Bruker 500 MHz): δ 1.06 (t,3H), 1.54 (s, 3H), 1.83 (t, 3H), 2.40 (q, 2H), 2.68 (s, 3H), 4.61 (d , 2H), 6.47 (s, 1H), 7.26-7.34 (m, 2H), 7.46-7.56 (m, 3H).

Synthesis example 2

[Formula 1n]

After dissolving the compound obtained in Synthesis Example 1 in ethanol, malononitrile and ammonium acetate were added, and the product was recrystallized to obtain a compound represented by Formula 1n.

MALD-TOF: 458.03 (M+), 475.22 (calculated) for C ₂₆ H ₂₆ BF ₂ N ₅ ,

¹ H NMR (CDCl, Bruker 500 MHz): δ 1.06 (t, 3H), 1.54 (s, 3H), 1.83 (t, 3H), 2.40 (q, 2H), 2.68 (s, 3H), 4.61 (d , 2H), 6.47 (s, 1H), 7.26-7.34 (m, 2H), 7.46-7.56 (m, 3H), 8.20 (s, 1H).

Synthesis example 3.

[Formula 1o]

After dissolving the compound obtained in Synthesis Example 1 in ethanol, piperidine and ethyl acetoacetate were added. Subsequently, the obtained product is refluxed for 4 hours, dried and recrystallized to obtain a compound represented by Formula 1o.

MALD-TOF: 475.21 (M+), 475.22 (calculated) for C ₂₇ H ₂₈ BF ₂ N ₃ O ₂ ,

¹ H NMR (CDCl, Bruker 500 MHz): δ 1.06 (t, 3H), 1.54 (s, 3H), 1.83 (t, 3H), 2.40 (q, 2H), 2.68 (s, 3H), 4.61 (d , 2H), 6.47 (s, 1H), 7.26-7.34 (m, 2H), 7.46-7.56 (m, 3H). 8.21 (s, 1H)

Synthesis example 4

[Formula 1p]

After dissolving the compound obtained in Synthesis Example 1 in absolute ethanol, piperidine and ethyl cyanoacetate were added. Subsequently, the obtained product is refluxed for 4 hours, dried and recrystallized to obtain a compound represented by Formula 1p.

MALD-TOF: 458.11 (M+), 458.21 (calculated) for C ₂₆ H ₂₅ BF ₂ N ₄ O,

¹ H NMR (CDCl, Bruker 500 MHz): δ 1.05 (t, 3H), 1.50 (s, 3H), 1.82 (t, 3H), 2.41 (q, 2H), 2.69 (s, 3H), 4.60 (d , 2H), 6.40 (s, 1H), 7.26-7.34 (m, 2H), 7.52-7.83 (m, 3H) 8.13 (s, 1H)

Synthesis example 5

[Formula 1j]

After dissolving the compound obtained in Synthesis Example 3 in ethanol, malononitrile and ammonium acetate were added, and the product was recrystallized to obtain a compound represented by Formula 1j.

MALD-TOF: 507.47 (M+), 506.22 (calculated) for C ₂₇ H ₂₈ BF ₂ N ₃ O ₂ ,

¹ H NMR (CDCl, Bruker 500 MHz): δ 1.05 (t, 3H), 1.50 (s, 3H), 1.82 (t, 3H), 2.41 (q, 2H), 2.69 (s, 3H), 4.60 (d , 2H), 6.40 (s, 1H), 7.26-7.34 (m, 2H), 7.52-7.83 (m, 3H), 7.89 (s, 1H).

Evaluation 1: Absorbance characteristic

The light absorption properties of the compounds obtained in Synthesis Examples 1 to 5 according to the wavelength were evaluated.

The light absorption characteristics were prepared by thermal evaporation of the compounds obtained in Synthesis Examples 1 to 5 at a rate of 0.1 to 1.0 Å/s under high vacuum (< 10 ^-7 Torr) to prepare a thin film having a thickness of 50 nm to 100 nm, and then the thin film was Cary 5000 Using UV spectroscopy (manufactured by Varian), it is evaluated by irradiating ultraviolet-visible light (UV-Vis).

The results are shown in Table 1.

Referring to Table 1, it can be seen that the compounds obtained in Synthesis Examples 1 to 5 have a maximum absorption wavelength (λ _max ) at about 500 nm to 600 nm and can selectively absorb light in a green wavelength region.

Maximum absorption wavelength (λmax, nm) Half width (nm) Synthesis Example 1 573 87 Synthesis Example 2 595 115 Synthesis Example 3 582 109 Synthesis Example 4 563 107 Synthesis Example 5 577 96

Evaluation 2: thin film properties

The thin film properties of the compound obtained in Synthesis Example 3 were evaluated.

Surface properties were prepared by thermal evaporation of the compound obtained in Synthesis Example 3 at a rate of 0.5 to 1.0 Å/s under high vacuum (< 10 ^-7 Torr) to form a 50 to 100 nm thick thin film, and then the thin film was subjected to atomic force microscope. force microscope) (Dimension V (Veeco Co.)).

5 is a photograph showing the thin film properties of the compound obtained in Synthesis Example 3.

Referring to FIG. 5, it can be seen that the compound obtained in Synthesis Example 3 formed a thin film having excellent single-film properties with an even surface.

Assessment 3: Energy level

The energy level of the compounds represented by the following formulas 1a to 1p is evaluated.

Energy level was calculated on a B3LYP/6-31G basis set by density functional theory (DFT) method using Gaussian software, and evaluated by AC-2 photoelectron spectrometer (Hitachi Co.).

[Formula 1a] [Formula 1b] [Formula 1c] [Formula 1d]

[Formula 1e] [Formula 1f] [Formula 1g]

[Formula 1h] [Formula 1i] [Formula 1j]

[Formula 1k] [Formula 1l] [Formula 1m] [Formula 1n]

[Formula 1o] [Formula 1p]

The results are shown in Table 2.

HOMO (eV) LUMO (eV) Band Gap (Eg, eV) Formula 1a -5.881 -2.799 3.082 Formula 1b -5.343 -2.702 2.641 Formula 1c -5.218 -2.703 2.515 Formula 1d -4.404 -1.921 2.483 Formula 1e -5.232 -2.292 2.94 Formula 1f -5.677 -3.279 2.398 Formula 1g -4.828 -2.780 2.048 Formula 1h -6.850 -4.119 2.731 Formula 1i -6.282 -3.300 2.982 Formula 1j -5.646 -3.489 2.157 Formula 1k -5.597 -3.042 2.555 Formula 1l -6.733 -4.112 2.621 Chemical formula 1m -5.132 -2.492 2.640 Formula 1n -5.404 -2.940 2.464 Formula 1o -5.632 -3.025 2.607 Formula 1p -5.644 -3.070 2.574

Referring to Table 2, it can be seen that the compounds represented by Formulas 1a to 1p have a HOMO level of about 4.3 to 7.0 eV and an energy band gap of about 1.9 to 3.1 eV.

abandonment Photoelectric Device fabrication

Example One

ITO is stacked on a glass substrate by sputtering to form an anode having a thickness of about 100 nm, and a molybdenum oxide (MoOx) thin film is laminated thereon as a charge auxiliary layer to a thickness of 30 nm. Subsequently, the compound according to Synthesis Example 3 (n-type semiconductor) and the compound (p-type semiconductor) represented by the following Formula 3a were co-deposited on a molybdenum oxide (MoOx) thin film in a 1:1 thickness ratio to form an active layer having a thickness of 70 nm. Subsequently, aluminum (Al) is laminated on the active layer by sputtering to form a cathode having a thickness of 80 nm, thereby fabricating an organic photoelectric device.

[Formula 3a]

Example 2

Instead of the compound (n-type semiconductor) according to Synthesis Example 3 and the compound (p-type semiconductor) represented by Formula 3a, a compound (n-type semiconductor) and a compound (p-type semiconductor) according to Synthesis Example 4 An organic photoelectric device was fabricated in the same manner as in Example 1, except that it was used.

[Formula 4]

Example 3

Instead of the compound according to Synthesis Example 3 (n-type semiconductor) and the compound represented by Formula 3a (p-type semiconductor), the compound according to Synthesis Example 4 (n-type semiconductor) and the compound (p-type semiconductor) represented by Formula 3a An organic photoelectric device was fabricated in the same manner as in Example 1, except that it was used.

Example 4

Instead of the compound according to Synthesis Example 3 (n-type semiconductor) and the compound represented by Formula 3a (p-type semiconductor), a compound (n-type semiconductor) according to Synthesis Example 4 and a compound (p-type semiconductor) represented by the following formula 2a An organic photoelectric device was fabricated in the same manner as in Example 1, except that it was used.

[Formula 2a]

Example 5

Instead of the compound according to Synthesis Example 3 (n-type semiconductor) and the compound represented by Formula 3a (p-type semiconductor), a compound (n-type semiconductor) according to Synthesis Example 4 and a compound (p-type semiconductor) represented by the following formula 2b An organic photoelectric device was fabricated in the same manner as in Example 1, except that it was used.

[Formula 2b]

Example 6

Instead of the compound according to Synthesis Example 3 (n-type semiconductor) and the compound represented by Formula 3a (p-type semiconductor), a compound (n-type semiconductor) according to Synthesis Example 4 and a compound (p-type semiconductor) represented by the following formula 2d An organic photoelectric device was fabricated in the same manner as in Example 1, except that it was used.

[Formula 2d]

Evaluation 4: External quantum efficiency ( EQE )

The external quantum efficiency (EQE) according to the wavelength and voltage of the organic photoelectric devices according to Examples 1 to 6 was evaluated.

External quantum efficiency is measured using the IPCE measurement system (McScience, Korea). First, after calibrating the facility using a Si photodiode (Hamamatsu, Japan), the organic photoelectric device according to Examples 1 to 6 was mounted on the facility, and the external quantum efficiency was measured in the wavelength range of about 350 to 750 nm. do.

6 to 11 are graphs showing external quantum efficiency (EQE) according to wavelength and voltage of organic photoelectric devices according to Examples 1 to 6, respectively.

6 to 11, it can be seen that the external quantum efficiency (EQE) is good in the green wavelength region of about 500 nm to 600 nm.

Evaluation 5: thermal stability

The thermal stability of the organic photoelectric devices according to Examples 4 and 5 was evaluated.

Thermal stability was evaluated from the change in current density after allowing the organic photoelectric devices according to Examples 4 and 5 to stand at 120° C. for 30 minutes.

12 is a graph showing a change in current density after allowing the organic photoelectric device according to Example 4 to stand at 120° C. for 30 minutes, and FIG. 13 is a graph showing the current density after leaving the organic photoelectric device according to Example 5 at 120° C. for 30 minutes. It is a graph showing the change in density.

12 and 13, the organic photoelectric device according to Examples 4 and 5 shows a phenomenon in which dark current decreases after being left at 120° C. for 30 minutes, and from this, it can be seen that the characteristics of the device are stabilized. Accordingly, it can be seen that the organic photoelectric devices according to Examples 4 and 5 do not deteriorate in performance and have high thermal stability even after being left at a high temperature.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention defined in the following claims are also present. It belongs to the scope of the invention.

10: first electrode 20: second electrode
30: active layer 40, 50: charge auxiliary layer
100: organic photoelectric device
300: organic CMOS image sensor

Claims (19)

A compound represented by any one of the following formulas 1d, 1e, 1f, 1g, 1h, 1j and 1n:
[Formula 1d] [Formula 1e] [Formula 1f]

[Formula 1g]

[Formula 1h] [Formula 1j] [Formula 1n]

In claim 1,
The compound is a compound having a maximum absorption wavelength (λ _max ) at 500nm to 600nm.
In claim 1,
The compound is a compound showing an absorption curve having a full width at half maximum (FWHM) of 50nm to 150nm in a thin film state.
In claim 1,
The compound has a HOMO level of 4.3 to 7.0 eV and an energy band gap of 1.9 to 3.1 eV.
delete delete A first electrode and a second electrode facing each other, and
An active layer positioned between the first electrode and the second electrode and containing a compound represented by the following formula (1)
Including,
The active layer exhibits an absorption curve having a maximum absorption wavelength (λ _max ) at 500 nm to 600 nm and a half width of 50 nm to 150 nm.
Organic photoelectric device:
[Formula 1]

In Formula 1,
R ¹ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted Ringed C3 to C30 heteroaryl group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C6 to C30 arylamine group, amine group, halogen group, hydroxy group, cyano group, cyanovinyl group, dicyano Vinyl group or a combination thereof,
R ² to R ⁷ are each independently present or two adjacent to each other form a fused ring, and hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 heterocycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heteroaryl group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C30 carbonyl group, substituted or unsubstituted C6 to C30 arylamine group, amine Group, halogen group, hydroxy group, cyano group, cyanovinyl group, dicyanovinyl group, or a combination thereof,
X ¹ and X ² are each independently a halogen group, a halogen-containing group, or a combination thereof,
In this case, at least one hydrogen is a halogen atom, a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group. , Carboxyl group, sulfonic acid group, phosphoric acid group, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C4 alkoxy group, C1 to C20 heteroalkyl group, C3 To C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, C6 to C15 cycloalkynyl group, C2 to C20 heterocycloalkyl group, or a combination thereof.
delete delete In clause 7,
The compound is an organic photoelectric device having a HOMO level of 4.3 to 7.0 eV and an energy band gap of 1.9 to 3.1 eV.
In clause 7,
X ¹ and X ² are each fluorine,
R ¹ is a substituted or unsubstituted C6 to C30 aryl group, a cyano group, or a combination thereof
Organic photoelectric device.
In clause 7,
The compound represented by Formula 1 is an organic photoelectric device represented by any one of the following Formulas 1b to 1h and 1j to 1p:
[Formula 1b] [Formula 1c] [Formula 1d]

[Formula 1e] [Formula 1f] [Formula 1g]

[Formula 1h] [Formula 1j]

[Formula 1k] [Formula 1l] [Formula 1m] [Formula 1n]

[Formula 1o] [Formula 1p]

In clause 7,
The active layer is an organic photoelectric device further comprising a p-type semiconductor compound or an n-type semiconductor compound.
In claim 13,
The p-type semiconductor compound is an organic photoelectric device comprising at least one of a compound represented by Formula 2 below and a compound represented by Formula 3 below:
[Formula 2]

In Chemical Formula 2,
R ⁸ to R ¹⁹ are Each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, substituted Or an unsubstituted C3 to C30 heteroaryl group, a substituted or unsubstituted C1 to C30 alkoxy group, a halogen atom, or a combination thereof,
In this case, at least one hydrogen is a halogen atom, a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group. , Carboxyl group, sulfonic acid group, phosphoric acid group, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C4 alkoxy group, C1 to C20 heteroalkyl group, C3 To C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, C6 to C15 cycloalkynyl group, C2 to C20 heterocycloalkyl group, or a combination thereof,
[Formula 3]

In Chemical Formula 3,
R ²⁰ to R ³¹ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, a halogen atom, a halogen-containing group Or a combination thereof,
X is an anion,
In this case, at least one hydrogen is a halogen atom, a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group. , Carboxyl group, sulfonic acid group, phosphoric acid group, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C4 alkoxy group, C1 to C20 heteroalkyl group, C3 To C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, C6 to C15 cycloalkynyl group, C2 to C20 heterocycloalkyl group, or a combination thereof.
In clause 7,
The active layer is an organic photoelectric device that selectively absorbs light in a green wavelength region.
In clause 7,
The active layer is an organic photoelectric device including an intrinsic layer including the compound represented by Chemical Formula 1.

In paragraph 16,
The active layer further comprises at least one of a p-type layer on one surface of the intrinsic layer and an n-type layer on the other surface of the intrinsic layer.
An image sensor comprising the organic photoelectric device according to any one of claims 7 and 10 to 17.
In paragraph 18,
A semiconductor substrate in which a plurality of first photo-sensing devices for sensing light in a blue wavelength region and a plurality of second photo-sensing devices for sensing light in a red wavelength region are integrated,
A color filter layer disposed on the semiconductor substrate and including a blue filter selectively absorbing light in a blue wavelength region and a red filter selectively absorbing light in a red wavelength region, and
The organic photoelectric device positioned above the color filter layer and selectively absorbs light in a green wavelength region
An image sensor comprising a.

Images